Note: Descriptions are shown in the official language in which they were submitted.
TITLE: SOLID CONTROLLED RELEASE CARBONATE DETERGENT
COMPOSITIONS
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims priority under 35 U.S.C. 119 to provisional
application
Serial No. 62/587,880, filed November 17, 2017, and to provisional application
Serial No.
62/490,959, filed April 27, 2017, both of which were titled "Slow Releasing
Ash Based
Detergent".
FIELD OF THE INVENTION
The invention relates to solid detergent compositions for dishwashing or
warewashing compositions and applications of use. In particular, the solid
carbonate-based
compositions that do not require a traditional dispenser, such as those that
dispense
chemistry on a per cycle basis, or a dispenser that controls a detergency
level in an
application, for controlled rate of release over multiple cycles. Instead, the
solid detergent
compositions are formulated to provide slow releasing or controlled releasing
of the
detergent composition, which does not require a dispensing system to control
the release of
the composition. In some embodiments, the solid detergent compsoitions can be
employed
as a daily detergent composition.
BACKGROUND OF THE INVENTION
Conventional detergents used in the vehicle care, food and beverage,
warewashing,
and laundry industries include alkaline detergents. Alkaline detergents,
particularly those
intended for institutional and commercial use, can contain various active
components to
solubilize preexisting inorganic salts and/or soils in the particular
application of use.
Various methods of dispensing conventional detergents are known, including the
use of
various dispensing systems and controlled release formulations designed to
provide solid
detergent offerings that can last for an extended period of time while
reducing the
occurrence of replacing the detergent composition in a dispenser and/or
employing a
dispenser.
In many standard or conventional applications of use a method of cleaning
wares
includes washing wares in a wash tub of an institutional warewashing machine
or a
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consumer dishwashing machine with at least one cycle that includes at least
one wash cycle
and at least one rinse cycle. Prior to or at the beginning of the cycle a
detergent
composition is dispensed from a dispenser of the warewashing or dishwashing
machine.
The detergents are typically added to an automated dispenser or delivery
device of an
institutional warewashing or consumer dishwashing machine prior to or at the
start of a
cycle. An automated dispenser is a device which controls a composition's
availability for
contact with water such that a composition is only available for contact with
water during a
specified period of the cycle.
There is a need in the art for an alternative, and preferably controlled
release
detergent composition that can be used in small footprint kitchens and/or
other locations
where traditional solid detergent dispensers are unavailable. Accordingly, it
is an objective
to develop a controlled release detergent composition, namely compositions and
methods
for a solid detergent offering in locations where traditional solid dispensers
are unavailable.
Other objects, advantages and features of the compositions and methods
disclosed herein
will become apparent from the following specification taken in conjunction
with the
accompanying drawings.
BRIEF SUMMARY OF THE INVENTION
An advantage of the compositions is that a solid controlled release alkaline
detergent composition can be provided without requiring a dispenser. In
embodiments, an
automated dispenser or delivery device is not required to dispense a solid
composition. It
is an advantage that homogenous solid compositions comprising a carbonate
alkalinity
source and at least one polysaccharide material provide desired controlled
release.
In an embodiment, compositions, cleaning systems and methods of use thereof.
While multiple embodiments are disclosed, still other embodiments will become
apparent
to those skilled in the art from the following detailed description, which
shows and
describes illustrative embodiments. Accordingly, the drawings and detailed
description are
to be regarded as illustrative in nature and not restrictive.
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. '
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a perspective view of an example holder for a solid controlled
release
tablet located inside an institutional warewashing machine.
FIG. 2 depicts the average number of total ware wash cycles that the solid
controlled release composition was utilized before being dissolved as a
function of the
concentration of the carboxylmethyl cellulose (CMC) evaluated as the
polysaccharide
material in the tablet according to embodiments of the compositions, methods
and systems.
FIG. 3 depicts the average number of total ware wash cycles that the solid
controlled release composition was utilized before being dissolved as a
function of the
concentration of the CMC evaluated as the polysaccharide material in the
tablet according
to embodiments of the compositions, methods and systems.
FIG. 4 shows the percent weight loss versus number of ware wash cycle of the
various controlled release compositions according to the concentration of the
CMC
evaluated as the polysaccharide material according to embodiments of the
compositions,
methods and systems.
FIG. 5 depicts the average number of total ware wash cycles the solid
controlled
release composition was utilized before being dissolved in comparison to the
concentration
of the xanthan gum evaluated as the polysaccharide material according to
embodiments of
the compositions, methods and systems.
FIG. 6 shows the percent weight loss versus number of ware wash cycles of the
various solid controlled release compositions according to the concentration
of the xanthan
gum evaluated as the polysaccharide material according to embodiments of the
compositions, methods and systems.
FIG. 7 depicts the average total number of ware wash cycles that solid
controlled
release compositions were utilized before being dissolved as a function of
degree of
substitution and viscosity of the polysaccharide materials in the tablet
according to
embodiments of the compositions.
FIG. 8 shows a tablet dispensing profile of a two-phase tablet compared to a
homogenous tablet, shown as concentration of the solid composition over time
with
different dispensing conditions according to embodiments of the compositions,
methods
and systems.
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= '
FIG. 9 shows images of both sides of a 2-phase tablet dispensed according to
embodiments of the compositions, methods and systems.
FIG. 10 depicts the number of cycles that the solid controlled release
composition
was utilized before being dissolved as a function of the concentration of the
carboxymethyl
cellulose (CMC) evaluated as the polysaccharide material in the tablet
according to
embodiments of the compositions as compared to the xanthan gum polysaccharide
material.
FIG. 11 depicts the number of cycles that the solid controlled release
composition
was utilized before being dissolved as a function of the degree of
substitution and the
viscosity of the carboxymethyl cellulose (CMC) polysaccharide material in the
tablet
according to embodiments of the compositions.
Various embodiments of the compositions, methods and systems will be described
in detail with reference to the drawings, wherein like reference numerals
represent like
parts throughout the several views. Reference to various embodiments does not
limit the
scope of the compositions, methods and systems. Figures represented herein are
not
limitations to the various embodiments and are presented for exemplary
illustration of the
compositions, methods and systems.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The embodiments are not limited to particular solid compositions and
dispensing
thereof, which can vary and are understood by skilled artisans. It is further
to be
understood that all terminology used herein is for the purpose of describing
particular
embodiments only, and is not intended to be limiting in any manner or scope.
For
example, as used in this specification and the appended claims, the singular
forms "a," "an"
and "the" can include plural referents unless the content clearly indicates
otherwise.
Further, all units, prefixes, and symbols may be denoted in its SI accepted
form. Numeric
ranges recited within the specification are inclusive of the numbers within
the defined
range. Throughout this disclosure, various aspects of the compositions,
methods and
systems are presented in a range format. It should be understood that the
description in
range format is merely for convenience and brevity and should not be construed
as an
inflexible limitation on the scope of the compositions, methods and systems.
Accordingly,
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the description of a range should be considered to have specifically disclosed
all the
possible sub-ranges as well as individual numerical values within that range
(e.g. 1 to 5
includes 1, 1.5, 2, 2.75, 3, 3.80, 4, and 5).
So that the present compositions, methods and systems may be more readily
understood, certain terms are first defined. Unless defined otherwise, all
technical and
scientific terms used herein have the same meaning as commonly understood by
one of
ordinary skill in the art to which embodiments pertain. Many methods and
materials
similar, modified, or equivalent to those described herein can be used in the
practice of the
embodiments without undue experimentation, but the preferred materials and
methods are
described herein. In describing and claiming the embodiments, the following
terminology
will be used in accordance with the definitions set out below.
The term "about," as used herein, refers to variation in the numerical
quantity that
can occur, for example, through typical measuring and liquid handling
procedures used for
making concentrates or use solutions in the real world; through inadvertent
error in these
procedures; through differences in the manufacture, source, or purity of the
ingredients
used to make the compositions or carry out the methods; and the like. The term
"about"
also encompasses amounts that differ due to different equilibrium conditions
for a
composition resulting from a particular initial mixture. Whether or not
modified by the
term "about", the claims include equivalents to the quantities.
The term "actives" or "percent actives" or "percent by weight actives" or
"actives
concentration" are used interchangeably herein and refers to the concentration
of those
ingredients involved in cleaning expressed as a percentage minus inert
ingredients such as
water or salts.
As used herein, the term "alkyl" or "alkyl groups" refers to saturated
hydrocarbons
having one or more carbon atoms, including straight-chain alkyl groups (e.g.,
methyl, ethyl,
propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, etc.), cyclic alkyl
groups (or
"cycloalkyl" or "alicyclic" or "carbocyclic" groups) (e.g., cyclopropyl,
cyclopentyl,
cyclohexyl, cycloheptyl, cyclooctyl, etc.), branched-chain alkyl groups (e.g.,
isopropyl, tert-
butyl, sec-butyl, isobutyl, etc.), and alkyl-substituted alkyl groups (e.g.,
alkyl-substituted
cycloalkyl groups and cycloalkyl-substituted alkyl groups). Unless otherwise
specified, the
term "alkyl" includes both "unsubstituted alkyls" and "substituted alkyls." As
used herein,
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the term "substituted alkyls" refers to alkyl groups having substituents
replacing one or
more hydrogens on one or more carbons of the hydrocarbon backbone. Such
substituents
may include, for example, alkenyl, alkynyl, halogeno, hydroxyl,
alkylcarbonyloxy,
arylcarbonyloxy, alkoxycarbonyloxy, aryloxy, aryloxycarbonyloxy, carboxylate,
alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aminocarbonyl,
alkylaminocarbonyl,
dialkylaminocarbonyl, alkylthiocarbonyl, alkoxyl, phosphate, phosphonato,
phosphinato,
cyano, amino (including alkyl amino, dialkylamino, arylamino, diarylamino, and
alkylarylamino), acylamino (including alkylcarbonylamino, arylcarbonylamino,
carbamoyl
and ureido), imino, sulfhydryl, alkylthio, arylthio, thiocarboxylate,
sulfates, alkylsulfinyl,
sulfonates, sulfamoyl, sulfonamido, nitro, trifluoromethyl, cyano, azido,
heterocyclic,
alkylaryl, or aromatic (including heteroaromatic) groups.
In some embodiments, substituted alkyls can include a heterocyclic group. As
used
herein, the term "heterocyclic group" includes closed ring structures
analogous to
carbocyclic groups in which one or more of the carbon atoms in the ring is an
element other
than carbon, for example, nitrogen, sulfur or oxygen. Heterocyclic groups may
be saturated
or unsaturated. Exemplary heterocyclic groups include, but are not limited to,
aziridine,
ethylene oxide (epoxides, oxiranes), thiirane (episulfides), dioxirane,
azetidine, oxetane,
thietane, dioxetane, dithietane, dithiete, azolidine, pyrrolidine, pyrroline,
oxolane,
dihydrofuran, and furan.
An "antiredeposition agent" refers to a compound that helps keep soil
suspended in
water instead of redepositing onto the object being cleaned. Antiredeposition
agents are
useful in the present compositions, methods and systems to assist in reducing
redepositing
of the removed soil onto the surface being cleaned.
As used herein, the term "cleaning" refers to a method used to facilitate or
aid in
soil removal, bleaching, microbial population reduction, and any combination
thereof. As
used herein, the term "microorganism" refers to any noncellular or unicellular
(including
colonial) organism. Microorganisms include all prokaryotes. Microorganisms
include
bacteria (including cyanobacteria), spores, lichens, fungi, protozoa, virinos,
viroids,
viruses, phages, and some algae. As used herein, the term "microbe" is
synonymous with
microorganism. For the purpose of this patent application, successful
microbial reduction
is achieved when the microbial populations are reduced by at least about 50%,
or by
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significantly more than is achieved by a wash with water. Larger reductions in
microbial
population provide greater levels of protection.
As used herein, the term "polymer" generally includes, but is not limited to,
homopolymers, copolymers, such as for example, block, graft, random and
alternating
copolymers, terpolymers, and higher "x"mers, further including their
derivatives,
combinations, and blends thereof. Furthermore, unless otherwise specifically
limited, the
term "polymer" shall include all possible isomeric configurations of the
molecule,
including, but are not limited to isotactic, syndiotactic and random
symmetries, and
combinations thereof. Furthermore, unless otherwise specifically limited, the
term
"polymer" shall include all possible geometrical configurations of the
molecule.
As used herein, the term "substantially free" refers to compositions
completely
lacking the component or having such a small amount of the component that the
component does not affect the performance of the composition. The component
may be
present as an impurity or as a contaminant and shall be less than 0.5 wt-%. In
another
embodiment, the amount of the component is less than 0.1 wt-% and in yet
another
embodiment, the amount of component is less than 0.01 wt-%.
The term "threshold agent" refers to a compound that inhibits crystallization
of
water hardness ions from solution, but that need not form a specific complex
with the water
hardness ion. Threshold agents include but are not limited to a polyacrylate,
a
polymethacrylate, an olefin/maleic copolymer, and the like.
As used herein, the term "ware" refers to items such as eating and cooking
utensils,
dishes, and other hard surfaces such as showers, sinks, toilets, bathtubs,
countertops,
windows, mirrors, transportation vehicles, and floors. As used herein, the
term
"warewashing" refers to washing, cleaning, or rinsing ware. Ware also refers
to items
made of plastic. Types of plastics that can be cleaned with the compositions
include but
not limited to those that include polypropylene polymers (PP), polycarbonate
polymers
(PC), melamine formaldehyde resins or melamine resin (melamine), acrylonitrile-
butadiene-styrene polymers (ABS), and polysulfone polymers (PS). Other
exemplary
plastics that can be cleaned using the compounds and compositions include
polyethylene
terephthalate (PET) polystyrene and polyamide.
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The term "weight percent," "wt-%," "percent by weight," "% by weight," and
variations thereof; as used herein, refer to the concentration of a substance
as the weight of
that substance divided by the total weight of the composition and multiplied
by 100. It is
understood that, as used here, "percent," "%," and the like are intended to be
synonymous
with "weight percent," "wt-%," etc.
The methods, systems, and compositions may comprise, consist essentially of,
or
consist of the components and ingredients as well as other ingredients
described herein. As
used herein, "consisting essentially of' means that the methods, systems, and
compositions
may include additional steps, components or ingredients, but only if the
additional steps,
components or ingredients do not materially alter the basic and novel
characteristics of the
claimed methods, systems, and compositions. It should also be noted that, as
used in this
specification and the appended claims, the term "configured" describes a
system, apparatus,
or other structure that is constructed or configured to perform a particular
task or adopt a
particular configuration. The term "configured" can be used interchangeably
with other
similar phrases such as arranged and configured, constructed and arranged,
adapted and
configured, adapted, constructed, manufactured and arranged, and the like.
Solid Compositions
In an aspect the solid ware wash compositions according to the disclosure
comprise,
consist of and/or consist essentially of a homogenous composition of an alkali
metal
alkalinity source, a polysaccharide material, at least one active ingredient
(e.g. surfactants
for cleaning and/or rinsing) and optionally additional functional ingredients.
In an aspect, the solid compositions do not include distinct or separate
components
thereof. The solid compositions are referred to as a single-part or a one-part
system. This is
beneficial and distinct from prior detergent compositions which are controlled
release as a
result of encapsulation, coating or membranes, separate dosing of components,
such as in
liquid formulations, or having distinct compartments for physical separation
of components
(sachets, pouches or the like) and must then be combined with a distinct
detergent
composition or other composition to provide the desired activity at the
controlled release
rate.
In some aspects, the solid compositions described herein can also include a
multi-
phase, such as a two-phase, or two or more solid phases, to increase the total
concentration
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of the detergent composition delivered over a desired number of cycles. In
such aspects,
there are multiple homogenous layers of the solid composition, wherein at
least one layer
comprises the polysaccharide materials, carbonate alkalinity source, and
active ingredient
cleaning agent. In another aspect, a first phase is a homogenous solid
comprising the
polysaccharide materials, carbonate alkalinity source, and active ingredient
cleaning agent,
and the second phase is also a homogenous solid comprising the carbonate
alkalinity source
and active ingredient cleaning agent. In each aspect, the first phase and/or
second phase can
further include the various additional functional ingredients. In an aspect,
the ratio of the
first phase to the second phase on weight basis is from about 10:1 to about
1:10, from
about 5:1 to about 1:5, from about 2:1 to about 1:2, or about 1:1 and is
modified to deliver
a desired concentration of cleaning agents. Such two-phase solids are distinct
from multi-
compartment solids and/or liquids (e.g. soluble packets or envelops or other
encapsulated
forms) or compressed and non-compressed formulations, as each of the two
phases are
homogenous solids with one phase containing the controlled (or also referred
to as slow)
release agents (the polysaccharide material) and the other phase not
containing the
controlled release agents (the polysaccharide material).
In an aspect of the embodiments, the solid compositions are designed to
release a
certain portion or amount of the solid composition in each cycle. In an
exemplary
embodiment, a warewashing cycle releases about 0 5 grams of the solid
composition per
cycle, about 1 gram of the solid composition per cycle, about 2 grams of the
solid
composition per cycle, about 5 grams of the solid composition per cycle, about
6 grams of
the solid composition per cycle, or about 10 grams of the solid composition
per cycle
(including all ranges therebetween). Accordingly, a skilled artisan will
ascertain from the
disclosure that the size of the solid composition can be suited for the number
of cycles run
on a daily basis (or other increment of time).
In an aspect, the solid compositions provide at least 5 cycles, at least 6
cycles, at
least 7 cycles, at least 8 cycles, at least 9 cycles, at least 10 cycles, at
least 15 cycles, at least
20 cycles, at least 25 cycles, at least 30 cycles, at least 35 cycles, at
least 40 cycles, or
greater for a 50 gram tablet. As one skilled in the art will ascertain, the
larger the solid
composition is formulated (e.g. 100 grams, 250 grams, or larger) an increase
in the number
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of cycles provided by the solid composition can be achieved and is included
within the
scope of the compositions, methods and systems.
In an aspect, the solid compositions provide at least 10 cycles, at least 11
cycles, at
least 12 cycles, at least 13 cycles, at least 14 cycles, at least 15 cycles,
at least 16 cycles, at
least 17 cycles, at least 18 cycles, at least 19 cycles, at least 20 cycles,
at least 25 cycles, at
least 30 cycles, at least 35 cycles, at least 40 cycles, at least 50 cycles,
at least 60 cycles, at
least 70 cycles, at least 80 cycles, at least 90 cycles, at least 100 cycles,
or greater for a 100
gram tablet.
Alkalinity Source
In an aspect the detergent compositions include an alkalinity source. In an
aspect,
the alkalinity source is selected from an alkali metal carbonate. Suitable
alkali metal
carbonates include, but are not limited to sodium carbonate or potassium
carbonate. In
aspects, the alkali metal carbonates are further understood to include
metasilicates,
silicates, bicarbonates and sesquicarbonates. Any "ash-based" or "alkali metal
carbonate"
composition shall also be understood to include all alkali metal carbonates,
metasilicates,
silicates, bicarbonates and/or sesquicarbonates.
In a preferred aspect, the alkalinity source is an alkali metal carbonate. In
further
preferred aspects, the alkaline cleaning compositions do not include organic
alkalinity
sources.
In an aspect, the compositions include from about 20 wt-% to about 95 wt-%
alkalinity source, from about 25 wt-% to about 90 wt-% alkalinity source, from
about 45
wt-% to about 90 wt-% alkalinity source, from about 50 wt-% to about 90 wt-%
alkalinity
source, from about 55 wt-% to about 85 wt-% alkalinity source, from about 30
wt-% to
= about 75 wt-% alkalinity source, from about 40 wt-% to about 75 wt-%
alkalinity source,
and preferably from about 45 wt-% to about 75 wt-% alkalinity source. In
addition, without
being limited according to the compositions, methods and systems, all ranges
recited are
inclusive of the numbers defining the range and include each integer within
the defined
range.
Polysaccharide Materials
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The solid ware wash compositions according to the disclosure include at least
one
polysaccharide material which has a desired measureable viscosity. In an
aspect, the
polysaccharide material can be a polysaccharide cellulosic material. In
another aspect, the
polysaccharide material can be a xanthan thickening material. In an aspect,
the
polysaccharide material can be a combination of more than one polysaccharide
cellulosic
material and a xanthan gum. In yet another aspect, the polysaccharide material
can be a
combination of a polysaccharide cellulosic material (or more than one
polysaccharide
cellulosic material) and a xanthan gum.
Examples of suitable cellulosic materials include, but are not limited to
carboxymethylcellulose (CMC), hydroxyethylcellulose (HEC),
hydroxypropylcellulose
(HPC), hydroxypropyl methylcelluslose (HPMC), methylcellulose (MC), cellulose
sulfate
esters, cellulose acetate, and cellulose triacetate. The cellulosic material
can function as a
solidification agent and as a controlled release agent. The cellulosic
material also functions
to regulate the amount of active ingredient that dissolves or diffuses into
the water. The
amount of active ingredient released is adjusted by modifying the components
of the
composition.
Additional suitable polysaccharide materials for use in the solid compositions
include, but are not limited to natural gums, including for example xanthan
gums (or
xanthum gums).
Additional suitable polysaccharide materials for use in the solid compositions
can
include, but are not limited to polysaccharides containing 3 or more
saccharide units.
Suitable saccharides include, but are not limited to glucose, fructose,
lactulose galactose,
raffinose, trehalose, sucrose, maltose, turanose, cellobiose, raffinose,
melezitose, maltriose,
acarbose, stachyose, ribose, arabinose, xylose, lyxose, deoxyribose, psicose,
sorbose,
tagatose, allose, altrose, mannose, gulose, idose, talose, fucose, fuculose,
rhamnose,
sedohepulose, octuse, nonose, erythrose, theose, amylose, amylopectin, pectin,
inulin,
modified inulin, potato starch, modified potato starch, corn starch, modified
corn starch,
wheat starch, modified wheat starch, rice starch, modified rice starch,
cellulose, modified
cellulose, dextrin, dextran, maltodextrin, cyclodextrin, glycogen and
oligiofructose, sodium
carboxymethylcellulose, linear sulfonated .alpha.-(1,4)-linked D-glucose
polymers,
.gamma.-cyclodextrin, amylose, modified inulin, potato starch, modified potato
starch, corn
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starch, modified corn starch, wheat starch, modified wheat starch, rice
starch, and modified
rice starch and the like.
One or more polysaccharide materials can be used in the solid compositions. In
some aspects a polysaccharide cellulosic material may prefrerably be used with
or in
combination with a xanthan gum.
In an embodiment, a combination of polysaccharide materials are used in the
solid
compositions. In an embodiment, at least two polysaccharide materials are used
in the solid
compositions.
In an embodiment, polysaccharide material(s) with a degree of polymerization
between about 200 and about 15,000, or preferably between about 200 and about
3,000 are
used in the solid compositions. In an embodiment, polysaccharide material(s)
with about a
1 wt-% aqueous solution viscosity (25 dC) between about 1 and about 5,000 cps,
or with a
2 wt-% aqueous solution viscosity (25 dC) between about 1 and about 5,000 cps
are used in
the solid compositions. In an embodiment, polysaccharide material(s) having a
degree of
substitution (D.S.) between zero and about 3, or preferably between about 0.5
and about
1.5 are used in the solid compositions.
In a preferred embodiment, polysaccharide material(s) in the solid
compositions
slow down or delay the dissolution of (and reduce the solubility of) the
hydroxide alkalinity
in the detergent composition and include polysaccharide material(s) with (a) a
degree of
.. polymerization between about 200 and about 15,000, or preferably between
about 200 and
about 3000, (b) between about a 1 wt-% to about a 2 wt-% aqueous solution
viscosity (25
dC) between about 1 and about 5000 cps, and/or (c) a degree of substitution
(D.S.) between
0 and about 3, or preferably between about 0.5 and about 1.5.
As referred to herein, a D.S. for polysaccharide material(s) indicates the
frequency
of carboxymethyl-, methyl-, ethyl-, hydroxyethyl-, hydroxypropyl-,
hydroxypropylmethyl-,
acetate-, triacetate-, acetate-propionate-, acetate-butyrate, and the like
groups attached to
each individual glucose unit of a cellulose molecule. In a still further
aspect, a D.S. for
polysaccharide material(s) can also refer to the substitution of one or more
of
carboxymethyl-, methyl-, ethyl-, hydroxyethyl-, hydroxypropyl-,
hydroxypropylmethyl-,
acetate-, triacetate-, acetate-propionate-, acetate-butyrate, and/or the like
groups attached to
each individual glucose unit of a cellulose molecule. Unexpectedly, the use of
the
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polysaccharide material(s) described herein for the solid compositions provide
the desired
slow-releasing characteristics through use of a relatively low polysaccharide
material
concentration, such as less than about 20% by weight of the solid composition.
Suitable concentrations for the polysaccharide material in the solid ware wash
composition can be between about 1% and about 20% by weight of the solid
composition.
Further suitable concentrations of polysaccharide material in the solid
compositions can be
between about 1% and about 15% by weight of the solid composition. Still
further suitable
concentrations of polysaccharide material in the solid compositions can be
between about
5% and about 20% by weight of the solid composition, or between about 5% and
about
15% by weight of the solid composition, or between about 10% and about 15% by
weight
of the solid composition, or between about 5% and about 10% by weight of the
solid
composition. A solid composition having too high of a polysaccharide material
content
may prevent a suitable amount of active ingredient from being added to the
composition
while a composition having not enough polysaccharide material will not provide
the
.. desired controlled release of the carbonate solid composition.
Water
Water may be independently added to the solid composition or may be provided
in
the composition as a result of its presence in an aqueous material that is
added to the solid
detergent composition. For example, materials added to the solid composition
may include
.. water or may be prepared in an aqueous premix. Typically, water is
introduced into the
composition to provide a desired viscosity for processing prior to
solidification and to
provide a desired rate of solidification. The water may also be present as a
processing aid
and may be removed or become water of hydration. The water may be added
separately as
deionized water, softened water, or hard water.
The amount of water in the resulting solid composition will depend on whether
the
solid composition is processed through forming techniques (including
solidification
through pressing), casting (solidification occurring within a container)
techniques, or other
solidification methods. In general, when the components are processed by
forming
techniques, the solid controlled release composition may include a smaller
amount of water
.. for solidification compared with the casting techniques. Suitable
concentrations of water
include between about 0 wt-% and about 20 wt-% of the solid composition.
Further
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suitable concentrations of water include between about 1 wt-% and about 20 wt-
%, or
between about 5 wt-% and about 20 wt-% of the solid composition.
Active Ingredient
The solid controlled release composition further includes at least one active
ingredient. The "active ingredient" can include a material that when dispersed
or dissolved
in a use and/or concentrate solution, such as an aqueous solution, provides a
beneficial
property in a particular use. Examples of active ingredients include but are
not limited to
chelants, enzymes, surfactants, and the like.
The compositions can be provided in any of a variety of embodiments. In an
embodiment, the detergent composition may be substantially free of
phosphorous,
nitriiotriacetic acid (NTA) and ethylenediaminetetraacetic acid (EDTA).
Phosphorus-free
means a composition having less than approximately 0.5 wt %, more
particularly, less than
approximately 0.1 wt %, and even more particularly less than approximately
0.01 wt %
phosphorous based on the total weight of the composition. NTA-free means a
composition
having less than approximately 0.5 wt %, less than approximately 0.1 wt %, and
particularly less than approximately 0.01 wt % NTA based on the total weight
of the
composition. When the composition is NTA-free, it is also compatible with
chlorine, which
functions as an anti-redeposition and stain-removal agent. When diluted to a
use solution,
the detergent composition includes phosphorous-containing components, NTA and
EDTA
concentrations of less than approximately 100 ppm, particularly less than
approximately 10
ppm, and more particularly less than approximately 1 ppm.
Surfactants
In an aspect, the detergent compositions may optionally include a defoaming
agent.
In a preferred aspect, the defoaming agent is a nonionic surfactant. In a
preferred aspect, the
defoaming agent is a nonionic alkoxylated surfactant. Exemplary suitable
alkoxylated
surfactants include ethylene oxide/propylene block copolymers (E0/P0
copolymers), such
as those available under the name Pluronic, capped EO/PO copolymers, alcohol
alkoxylates, capped alcohol alkoxylates, mixtures thereof, or the like.
In an aspect, the detergent compositions include a combination of surfactants
to
provide good cleanability and rinseability. In an embodiment, the surfactants
of the
detergent compositions include at least two nonionic surfactants. In
embodiment, the
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. .
nonionic surfactants comprise an alcohol alkoxylate and an EO/PO copolymer. In
an
alternative embodiment, the nonionic surfactants comprise an alcohol
alkoxylate and an
alkyl alkoxylate. In a still further embodiment, the nonionic surfactants are
selected from
the group consisting of an alcohol alkoxylate, an alkyl alkoxylate, an EO/PO
copolymer,
and combinations thereof. In some embodiments, the ratio of the alcohol
alkoxylate to the
alkyl alkoxylate (preferably EO/PO copolymer) is preferably from about 1:5 to
about 5:1,
more preferably from about 1:3 to about 3:1, and most preferably from about
1:2 to about
2:1. In an exemplary embodiment, the nonionic surfactants include an alkyl
alkoxylate
(preferably EO/PO copolymer) and alcohol alkoxylate in a ratio of about 1:1,
from about
1:5 to about 5:1, from about 1:3 to about 3:1, or from about 1:2 to about 2:1.
In a preferred
aspect, the alkaline detergent composition includes an alkyl alkoxylate
(preferably EO/PO
copolymer) and alcohol alkoxylate in a ratio of about 1:1.
Suitable alcohol alkoxylates include ethylene oxide, propylene oxide, and
butylene
oxide groups and mixtures thereof. Particularly, suitable alcohol alkoxylates
can have
between about 1 and about 30 moles of alkyl oxide and carbon chains between
about 4 and
about 20 carbons in length. In a preferred embodiment the alcohol ethoxylate
may be a
C8¨C18 alcohol alkoxylate with about 10 to about 40 moles of alkyl oxide. In a
more
preferred embodiment the alcohol alkoxylate may be a C8¨C16-alcohol alkoxylate
with
about 10 to about 30 moles of alkyl oxide. In an even more preferred
embodiment, the
alcohol alkoxylate may be a C10¨C12 alcohol alkoxylate with about 15 to about
25 moles
of alkyl oxide. Examples of preferred alcohol alkoxylates are available under
the brands
Surfonic (available from Huntsman), Rhodasurf (available from Rhodia), Novel
(available
from Sasol), Lutensol (available from BASF).
Alkyl alkoxylates having ethylene oxide/propylene oxide derivatives or
copolymer
(E0/P0) copolymer surfactant are particularly suitable for the alkaline
compositions. The
EO/PO copolymer may have from about 1 to about 50 moles of EO and from about 1
to
about 50 moles of PO. In a preferred embodiment, the EO/PO copolymer is a
block
polymer. In another aspect, the EO/PO copolymer does not contain a C8-18 alkyl
group, or
even any alkyl groups.
These EO/PO copolymer surfactants can include a compact alcohol EO/PO
= surfactant where the EO and PO groups are in small block form, or random
form. In other
CA 3060312 2019-10-29
embodiments, the alkyl alkoxylate includes an ethylene oxide, a propylene
oxide, a
butylene oxide, a pentalene oxide, a hexylene oxide, a heptalene oxide, an
octalene oxide, a
nonalene oxide, a decylene oxide, and mixtures thereof. The alkyl group can be
C10-C18,
linear or branched. In an aspect, the EO/PO copolymer surfactants are
particularly suitable
for use in the 2-in-1 alkaline compositions in combination with an alcohol
alkoxylate
surfactant. Exemplary commercially available surfactants are available, for
example, under
the tradename Pluronic0 and Pluronic R, (commercially available from BASF),
Tetronic
(available from Dow) and Surfonic (available from Huntsman).
Some examples of ethylene oxide and/or propylene oxide derivative surfactants
that
may be used include polyoxyethylene-polyoxypropylene block copolymers, or the
like, or
derivatives thereof. Some examples of polyoxyethylene-polyoxypropylene block
copolymers include those having the following formulae:
(E0)x(PO)y(E0)x
(PO)y(E0)x(PO)y
(POVE0)x(PO)y(E0) x(P0) y
wherein EO represents an ethylene oxide group, PO represents a propylene oxide
group,
and x and y reflect the average molecular proportion of each alkylene oxide
monomer in
the overall block copolymer composition. In an aspect, a preferred EO/PO
copolymer is
represented by the formula (E0)x(PO)y(E0)x. In a further aspect, a preferred
EO/PO
copolymer is represented by the formula (PO)y(E0)x(PO)y. In some embodiments,
x is in
the range of about 5 to about 50, y is in the range of about 1 to about 50,
and x plus y is in
the range of about 6 to about 200. It should be understood that each x and y
in a molecule
can be different. In some embodiments, the material can have a molecular
weight greater
than about 200 and less than about 25,000. For example, in some embodiments,
the
material can have a molecular weight in the range of about 500 to about
25,000, or in the
range of about 1000 to about 20,000.
In some embodiments, the EO/PO surfactants may have between about 1 and about
50 ethylene oxide groups and from about 1 to about 50 propylene oxide groups.
In some
embodiments, the material can have a molecular weight greater than about 400,
and in
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some embodiments, greater than about 500. For example, in some embodiments,
the
material can have a molecular weight (g/mol) in the range of about 500 to
about 7000 or
more, or in the range of about 950 to about 4000 or more, or in the range of
about 1000 to
about 3100 or more, or in the range of about 2100 to about 6700 or more, or in
the range of
about 2500 to about 4200 or more.
The treatise Nonionic Surfactants, edited by Schick, M. J., Vol. 1 of the
Surfactant
Science Series, Marcel Dekker, Inc., New York, 1983 provides further
description of
nonionic compounds generally employed. A typical listing of nonionic classes,
and species
of these surfactants, is given in U.S. Pat. No. 3,929,678 issued to Laughlin
and Heuring on
Dec. 30, 1975. Further examples are given in "Surface Active Agents and
detergents" (Vol.
I and II by Schwartz, Perry and Berch).
The various nonionic surfactants can further be combined with polymers
suitable
for detergent compositions, including those disclosed in U.S. patent No.
9,796,947.
Other defoaming agents can include silicone compounds such as silica dispersed
in
polydimethylsiloxane, polydimethylsiloxane, and functionalized
polydimethylsiloxane such
as those available under the name Abil B9952, fatty amides, hydrocarbon waxes,
fatty
acids, fatty esters, fatty alcohols, fatty acid soaps, ethoxylates, mineral
oils, polyethylene
glycol esters, alkyl phosphate esters such as monostearyl phosphate, and the
like. A
discussion of defoaming agents may be found, for example, in U.S. Pat. No.
3,048,548 to
Martin et at., U.S. Pat. No. 3,334,147 to Brunelle et al., and U.S. Pat. No.
3,442,242 to Rue
et al.
Nonionic surfactants generally characterized by the presence of an organic
hydrophobic group and an organic hydrophilic group and are typically produced
by the
condensation of an organic aliphatic, alkyl aromatic or polyoxyalkylene
hydrophobic
compound with a hydrophilic alkaline oxide moiety which in common practice is
ethylene
oxide or a polyhydration product thereof, polyethylene glycol. Practically any
hydrophobic
compound having a hydroxyl, carboxyl, amino, or amido group with a reactive
hydrogen
atom can be condensed with ethylene oxide, or its polyhydration adducts, or
its mixtures
with alkoxylenes such as propylene oxide to form a nonionic surface-active
agent. The
length of the hydrophilic polyoxyalkylene moiety which is condensed with any
particular
hydrophobic compound can be readily adjusted to yield a water dispersible or
water soluble
17
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compound having the desired degree of balance between hydrophilic and
hydrophobic
properties. According to the compositions, methods and systems, the nonionic
surfactant
useful in the composition is a low-foaming nonionic surfactant. Examples of
nonionic low
foaming surfactants useful include:
Block polyoxypropylene-polyoxyethylene polymeric compounds based upon
propylene glycol, ethylene glycol, glycerol, trimethylolpropane, and
ethylenediamine as the
initiator reactive hydrogen compound. Examples of polymeric compounds made
from a
sequential propoxylation and ethoxylation of initiator are commercially
available under the
trade names Pluronic and Tetronico manufactured by BASF Corp. Pluronic
compounds
are difunctional (two reactive hydrogens) compounds formed by condensing
ethylene oxide
with a hydrophobic base formed by the addition of propylene oxide to the two
hydroxyl
groups of propylene glycol. This hydrophobic portion of the molecule weighs
from 1,000
to 4,000. Ethylene oxide is then added to sandwich this hydrophobe between
hydrophilic
groups, controlled by length to constitute from about 10% by weight to about
80% by
weight of the final molecule. Tetronic compounds are tetra-functional block
copolymers
derived from the sequential addition of propylene oxide and ethylene oxide to
ethylenediamine. The molecular weight of the propylene oxide hydrotype ranges
from 500
to 7,000; and, the hydrophile, ethylene oxide, is added to constitute from 10%
by weight to
80% by weight of the molecule.
Condensation products of one mole of alkyl phenol wherein the alkyl chain, of
straight chain or branched chain configuration, or of single or dual alkyl
constituent,
contains from 8 to 18 carbon atoms with from 3 to 50 moles of ethylene oxide.
The alkyl
group can, for example, be represented by diisobutylene, di-amyl, polymerized
propylene,
iso-octyl, nonyl, and di-nonyl. These surfactants can be polyethylene,
polypropylene, and
polybutylene oxide condensates of alkyl phenols. Examples of commercial
compounds of
this chemistry are available on the market under the trade names Igepal
manufactured by
Rhone-Poulenc and Triton manufactured by Dow.
Condensation products of one mole of a saturated or unsaturated, straight or
branched chain alcohol having from 6 to 24 carbon atoms with from 3 to 50
moles of
ethylene oxide. The alcohol moiety can consist of mixtures of alcohols in the
above
delineated carbon range or it can consist of an alcohol having a specific
number of carbon
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CA 3060312 2019-10-29
atoms within this range. Examples of like commercial surfactant are available
under the
trade names Neodol manufactured by Shell Chemical Co. and Alfonic
manufactured by
Vista Chemical Co.
Condensation products of one mole of saturated or unsaturated, straight or
branched
chain carboxylic acid having from 8 to 18 carbon atoms with from 6 to 50 moles
of
ethylene oxide. The acid moiety can consist of mixtures of acids in the above
defined
carbon atoms range or it can consist of an acid having a specific number of
carbon atoms
within the range. Examples of commercial compounds of this chemistry are
available on
the market under the trade names Nopalcol manufactured by Henkel Corporation
and
Lipopeg manufactured by Lipo Chemicals, Inc.
Compounds with the following structure:
RO-(PO)o-5(E0)1-30 (P0)1-30
Wherein R is a C8-18 linear or branched alkyl group; E0=ethylene oxide;
PO=propylene oxide
Compounds from (1) which are modified, essentially reversed, by adding
ethylene
oxide to ethylene glycol to provide a hydrophile of designated molecular
weight; and, then
adding propylene oxide to obtain hydrophobic blocks on the outside (ends) of
the molecule.
The hydrophobic portion of the molecule weighs from 1,000 to 3,100 with the
central
hydrophile including 10% by weight to 80% by weight of the final molecule.
These
.. reverse Pluronics are manufactured by BASF Corporation under the trade
name
Pluronic R surfactants.
Alkoxylated diamines produced by the sequential addition of propylene oxide
and
ethylene oxide to ethylenediamine. The hydrophobic portion of the molecule
weighs from
250 to 6,700 with the central hydrophile including 0.1% by weight to 50% by
weight of the
final molecule. Examples of commercial compounds of this chemistry are
available from
BASF Corporation under the tradename TetronicT" Surfactants.
Alkoxylated diamines produced by the sequential addition of ethylene oxide and
propylene oxide to ethylenediamine. The hydrophobic portion of the molecule
weighs
from 250 to 6,700 with the central hydrophile including 0.1% by weight to 50%
by weight
of the final molecule. Examples of commercial compounds of this chemistry are
available
from BASF Corporation under the tradename Tetronic RTM Surfactants.
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Compounds which are modified by "capping" or "end blocking" the terminal
hydroxy group or groups (of multi-functional moieties) to reduce foaming by
reaction with
a small hydrophobic molecule such as propylene oxide, butylene oxide, benzyl
chloride;
and, short chain fatty acids, alcohols or alkyl halides containing from 1 to 5
carbon atoms;
and mixtures thereof. Also included are reactants such as thionyl chloride
which convert
terminal hydroxy groups to a chloride group. Such modifications to the
terminal hydroxy
group may lead to all-block, block-heteric, heteric-block or all-heteric
nonionics.
Polyoxyalkylene surface-active agents which are advantageously used in the
compositions correspond to the formula: P[(C3H60)4C21140)mH]x wherein P is the
residue
of an organic compound having from 8 to 18 carbon atoms and containing x
reactive
hydrogen atoms in which x has a value of 1 or 2, n has a value such that the
molecular
weight of the polyoxyethylene portion is at least 44 and m has a value such
that the
oxypropylene content of the molecule is from 10% to 90% by weight. In either
case the
oxypropylene chains may contain optionally, but advantageously, small amounts
of
ethylene oxide and the oxyethylene chains may contain also optionally, but
advantageously,
small amounts of propylene oxide.
Alkoxylated amines or, most particularly, alcohol
alkoxylated/aminated/alkoxylated
surfactants. These non-ionic surfactants may be at least in part represented
by the general
formulae:
le--(P0),INI-(E0)t H,
R20--(P0) N-(E0) t H(E0) t H, and
R2 --N(E0) t H;
in which R2 is an alkyl, alkenyl or other aliphatic group, or an alkyl-aryl
group of from 8 to
20, preferably 12 to 14 carbon atoms, EO is oxyethylene, PO is oxypropylene, s
is 1 to 20,
preferably 2-5, t is 1-10, preferably 2-5, and u is 1-10, preferably 2-5.
Other variations on
the scope of these compounds may be represented by the alternative formula:
R20-
-(PO) (PO) ,--N[(EO)w H][(E0)2H]
in which R2 is as defined above, v is 1 to 20 (e.g., 1, 2, 3, or 4
(preferably 2)), and w and z
are independently 1-10, preferably 2-5. These compounds are represented
commercially by
.. a line of products sold by Huntsman Chemicals as nonionic surfactants. A
preferred
chemical of this class includes Surfonic PEA 25 Amine Alkoxylate.
CA 3060312 2019-10-29
Suitable amounts of the nonfoaming nonionic surfactant include between about
0.01% and about 15% by weight of the cleaning solution. Particularly suitable
amounts
include between about 0.1% and about 12% or between about 0.5% and about 10%
by
weight of the cleaning solution.
Additional Functional Ingredients
The components of the detergent composition can further be combined with
various
functional components suitable for use in ware wash applications. In some
embodiments
few or no additional functional ingredients are disposed therein. In other
embodiments,
additional functional ingredients may be included in the compositions. The
functional
ingredients provide desired properties and functionalities to the
compositions. For the
purpose of this application, the term "functional ingredient" includes a
material that when
dispersed or dissolved in a use and/or concentrate solution, such as an
aqueous solution,
provides a beneficial property in a particular use. Some particular examples
of functional
materials are discussed in more detail below, although the particular
materials discussed
are given by way of example only, and that a broad variety of other functional
ingredients
may be used. For example, many of the functional materials discussed below
relate to
materials used in cleaning, specifically ware wash applications. However,
other
embodiments may include functional ingredients for use in other applications.
In some embodiments, the compositions may include enzymes, defoaming agents,
anti-redeposition agents, anti-scale agents, bleaching agents, solubility
modifiers,
dispersants, metal protecting agents, stabilizing agents, corrosion
inhibitors, additional
sequestrants and/or chelating agents, threshold inhibitors, crystal modifiers,
fragrances
and/or dyes, rheology modifiers or thickeners, hydrotropes or couplers,
buffers, solvents
and the like. The compositions may include from about 0 wt-% to about 50 wt-%,
from
about 0.01 wt-% to about 50 wt-%, from about 0.1 wt-% to about 50 wt-%, from
about 1
wt-% to about 50 wt-%, from about 1 wt-% to about 40 wt-%, from about 1 wt-%
to about
wt-%, from about I wt-% to about 25 wt-%, from about 5 wt-% to about 25 wt-%,
or
from about 5 wt-% to about 20 wt-% additional functional ingredients. The
composition
can include one or more building agents, also called chelating or sequestering
agents (e.g.,
30 builders), including, but not limited to: condensed phosphates, alkali
metal carbonates,
phosphonates, aminocarboxylic acids, and/or polyearboxylic acids. In general,
a chelating
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agent is a molecule capable of coordinating (i.e., binding) the metal ions
commonly found
in natural water to prevent the metal ions from interfering with the action of
the other
detersive ingredients of a cleaning composition. Preferable levels of addition
for builders
that can also be chelating or sequestering agents are between about 0.1% to
about 70% by
weight, about 1% to about 60% by weight, or about 1.5% to about 50% by weight.
Additional ranges of the builders include between approximately 3% to
approximately 20%
by weight, between approximately 6% to approximately 15% by weight, between
approximately 25% to approximately 50% by weight, and between approximately
35% to
approximately 45% by weight.
Examples of suitable anti-scale agents, threshold inhibitors, and dispersants
include
aminocarboxylates. Suitable aminocarboxylates include, for example, N-
hydroxyethylaminodiacetic acid, ethylenediaminetetraacetic acid (EDTA),
methylglycinediacetic acid (MGDA), hydroxyethylenediaminetetraacetic acid,
diethylenetriaminepentaacetic acid, N-hydroxyethyl-ethylenediaminetriacetic
acid
(HEDTA), glutamic acid N,N-diacetic acid (GLDA), diethylenetriaminepentaacetic
acid
(DTPA), and other similar acids having an amino group with a carboxylic acid
substituent
Beneficially, the aminocarboxylates provide a strong cleaning performance
while
employing chelants that are substantially free of NTA-containing compounds,
making the
detergent composition more environmentally acceptable. Useful aminocarboxylic
acid
materials containing little or no NTA include, but are not limited to: N-
hydroxyethylaminodiacetic acid, ethylenediaminetetraacetic acid (EDTA),
hydroxyethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, N-
hydroxyethyl-ethylenediaminetriacetic acid (HEDTA),
diethylenetriaminepentaacetic acid
(DTPA), methylglycinediacetic acid (MGDA), glutamic acid-N,N-diacetic acid
(GLDA),
ethylenediaminesuccinic acid (EDDS), 2-hydroxyethyliminodiacetic acid (HETDA),
iminodisuccinic acid (IDS), 3-hydroxy-2-2'-iminodisuccinic acid (HIDS) and
other similar
acids or salts thereof having an amino group with a carboxylic acid
substituent. In one
embodiment, however, the detergent composition is free of aminocarboxylates.
Examples of condensed phosphates include, but are not limited to: sodium and
potassium orthophosphate, sodium and potassium pyrophosphate, sodium
tripolyphosphate, and sodium hexametaphosphate. A condensed phosphate may also
assist,
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to a limited extent, in solidification of the detergent composition by fixing
the free water
present in the detergent composition as water of hydration. In some
embodiments, the
compositions include a phosphonate. Examples of phosphonates include, but are
not
limited to: phosphinosuccinic acid oligomer (PSO) described in US patents
8,871,699 and
9,255,242; 2-phosphinobutane-1,2,4-tricarboxylic acid (PBTC), 1-hydroxyethane-
1,1-
diphosphonic acid, CH2C(OH)[PO(OH)2]2; aminotri(methylenephosphonic acid),
N[CH2PO(OH)2]3; am inotri(methylenephosphonate). sodium salt (ATMP).
N[CH2P0(0Na)2]3; 2-hydroxyethyliminobis(methylenephosphonic acid),
HOCH2CH2N[CH2P0(OH)2]2; diethylenetriaminepenta(methylenephosphonic acid),
(H0)2POCH2N[CH2CH2N[CH2P0(OH)2]212;
diethylenetriaminepenta(methylenephosphonate), sodium salt (DTPMP), C9H(28-
x)1\13Nax015P5- (x=7); hexamethylenediamine(tetramethylenephosphonate),
potassium salt,
CloH(28_,)N2K,,012P4(x=6); bis(hexamethylene)triamine(pentamethylenephosphonic
acid),
(H02)POCH2NRCH2)2N[CH2PO(OH)2]2]2; monoethanolamine phosphonate (MEAP);
diglycolamine phosphonate (DGAP) and phosphorus acid, H3P03. Preferred
phosphonates
are PBTC, HEDP, ATNIP and DTPMP. A neutralized or alkali phosphonate, or a
combination of the phosphonate with an alkali source prior to being added into
the mixture
such that there is little or no heat or gas generated by a neutralization
reaction when the
phosphonate is added is preferred. In one embodiment, however, the composition
is
phosphorous-free. Suitable amounts of the phosphonates include between about
0% and
about 25% by weight of the composition, between about 0.1% and about 20%, or
between
about 0.5% and about 15% by weight of the composition.
Additional water conditioning polymers can also be referred to as non-
phosphorus
containing builders. Additional water conditioning polymers may include, but
are not
limited to: polycarboxylates. Exemplary polycarboxylates that can be used as
builders
and/or water conditioning polymers include, but are not limited to: those
having pendant
carboxylate (--0O2-) groups such as polyacrylic acid homopolymers, polymaleic
acid
homopolymers, maleic/olefin copolymers, sulfonated copolymers or terpolymers,
acrylic/maleic copolymers or terpolymers polymethacrylic acid homopolymers,
polymethacrylic acid copolymers or terpolymers, acrylic acid-methacrylic acid
copolymers,
hydrolyzed polyacrylamides, hydrolyzed polymethacrylamides, hydrolyzed
polyamide-
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methacrylamide copolymers, hydrolyzed polyacrylonitriles, hydrolyzed
polymethacrylonitriles, hydrolyzed acrylonitrile-methacrylonitrile copolymers
and
combinations thereof For a further discussion of chelating
agents/sequestrants, see Kirk-
Othmer, Encyclopedia of Chemical Technology, Third Edition, volume 5, pages
339-366
and volume 23, pages 319-320. These materials may also be used at sub
stoichiometric
levels to function as crystal modifiers.
Enzymes
The solid alkaline compositions can further include an
enzyme to provide enhanced removal of soils, prevention of redeposition and
additionally
the reduction of foam in use solutions of the cleaning compositions. The
purpose of the
enzyme is to break down adherent soils, such as starch or proteinaceous
materials, typically
found in soiled surfaces and removed by a detergent composition into a wash
water source.
The enzyme compositions remove soils from substrates and prevent redeposition
of soils
on substrate surfaces. Enzymes provide additional cleaning and detergency
benefits, such
as anti-foaming.
Exemplary types of enzymes which can be incorporated into detergent
compositions
or detergent use solutions include amylase, protease, lipase, cellulase,
cutinase, gluconase,
peroxidase and/or mixtures theleof. An enzyme composition may employ more than
one
enzyme, from any suitable origin, such as vegetable, animal, bacterial, fungal
or yeast
origin. However, according to a preferred embodiment, the enzyme is a
protease. As used
herein, the terms "protease" or "proteinase" refer enzymes that catalyze the
hydrolysis of
peptide bonds.
As one skilled in the art shall ascertain, enzymes are designed to work with
specific
types of soils. For example, according to an embodiment, ware wash
applications may use
a protease enzyme as it is effective at the high temperatures of the ware wash
machines and
is effective in reducing protein-based soils. Protease enzymes are
particularly advantageous
for cleaning soils containing protein, such as blood, cutaneous scales, mucus,
grass, food
(e.g., egg, milk, spinach, meat residue, tomato sauce), or the like. Protease
enzymes are
capable of cleaving macromolecular protein links of amino acid residues and
convert
.. substrates into small fragments that are readily dissolved or dispersed
into the aqueous use
solution. Proteases are often referred to as detersive enzymes due to the
ability to break
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soils through the chemical reaction known as hydrolysis. Examples of
commercially-
available protease enzymes are available under the following trade names:
EsperaseTM,
PurafectTM, Purafect LTM, Purafect OxTM, EverlaseTM, LiquanaseTM, SavinaseTM,
Prime LTM,
ProsperaseTM and BlapTM.
Additional description of enzyme compositions suitable for use is disclosed
for
example in U.S. Patents Nos. 7,670,549, 7,723,281, 7,670,549, 7,553,806,
7,491,362,
6,638,902, 6,624,132, and 6,197,739 and U.S. Patent Publication Nos.
2012/0046211 and
2004/0072714. In addition, the reference "Industrial Enzymes", Scott, D., in
Kirk-Othmer
Encyclopedia of Chemical Technology, 3rd Edition, (editors Grayson, M. and
EcKroth, D.)
Vol. 9, pp. 173-224, John Wiley & Sons, New York, 1980.
In a preferred aspect, the enzyme compositions are provided in a solid
composition in
an amount between about 0.01 wt-% to about 40 wt-%, between about 0.01 wt-% to
about 30
wt-%, between about 0.01 wt-% to about 10 wt-%, between about 0.1 wt-% to
about 5 wt-%,
and preferably between about 0.2 wt-% to about 1 wt-%.
Embodiments
Exemplary ranges of the solid ware wash compositions are shown in Table 1 in
weight percentage of the solid detergent compositions.
TABLE 1
Material First Second Third Fourth
Exemplary Exemplary Exemplary Exemplary
Range wt- Range wt- Range wt- Range wt-
%
Alkalinity Source 20-95 45-90 50-90 55-85
Polysaccharide material 0.01-40 0.1-30 1-30 1-20
Additional polysaccharides 0-10 0.1-10 0.1-7.5 1-5
Active Ingredient (e.g. 0.1-40 0.5-40 1-30 1-10
surfactant)
Additional Functional 0-50 0A-50 1-40 1-25
Ingredients
Date Recue/Date Received 2021-03-25
The solid ware wash compositions can be provided in various product forms. Any
suitable product form can be used as described herein. Suitable product forms
include, but
are not limited to: capsules, tablets, coated tablets, pucks, brick, block,
and combinations
thereof. In a preferred aspect, the solid controlled release composition is a
substantially
homogenous composition and can be in block, tablet or capsule form.
The solid ware wash compositions can be provided in various product sizes,
including, for example a solid having a mass of at least about 25 grams, at
least about 50
grams, at least about 100 grams, at least about 250 grams, at least about 500
grams, at least
about 1000 grams, or greater. It should be understood that the concentration
of the active
components in the solid ware wash composition will vary depending on the
dilution rate of
the concentrate solid ware wash composition. Beneficially, the solid detergent
compositions are dispensed directly into the use solution to create a
concentrated use
solution.
In an aspect, the detergent composition preferably provides efficacious
cleaning by
diluting the solid concentrate with water at a dilution ratio that provides a
use solution
having desired detersive properties. The water that is used to dilute the
concentrate to form
the use composition can be referred to as water of dilution or a diluent, and
can vary from
one location to another. The typical dilution factor is between approximately
1 and
approximately 10,000 but will depend on factors including water hardness, the
amount of
soil to be removed and the like. In an embodiment, the concentrate is diluted
at a ratio of
between about 1:10 and about 1:10,000 concentrate to water. Particularly, the
concentrate
is diluted at a ratio of between about 1:100 and about 1:5,000 concentrate to
water. More
particularly, the concentrate is diluted at a ratio of between about 1:250 and
about 1:2,000
concentrate to water.
Cleaning Systems
In an aspect, a cleaning system comprising the solid controlled release
composition
and a holder (such as shown in FIG. 1), wherein the holder configured to hold
the solid
composition and configured to be secured to a wash tub of a warewashing or
dishwashing
machine. The holder can comprise a mesh, basket, cage, net cartridge or case.
Beneficially,
the solid controlled release composition does not require a conventional
dispenser. As
depicted in FIG. 1 an examplary holder 10 is located in wash tub 12 of a
warewashing
26
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. = .
machine. Portions of wash tub 12 have been broken away. Hanger 14 secures
holder 10 to a
support of the warewashing machine. Solid controlled release tablet 16 is
placed within
holder 10. Holder 10 can have any suitable shape which supports solid
controlled release
tablet 16. For example, holder 10 can have a bottom and sides and an open top.
Holder 10
is configured to allow water to enter and exit. For example, holder 10 may be
formed from
a mesh in which voids allow water to enter and exit the holder. In use, water
enters holder
and contacts solid controlled release tablet 16 which releases a portion of
the active
ingredient into the water to form a use solution. The use solution leaves
holder 10 and
contacts wares in the wash tub. Holder 10 is strong enough to support
controlled release
10 tablet 16 while allowing a sufficient amount of water to contact solid
controlled release
tablet 16.
The holder can be removably or non-removably attached to the solid controlled
release composition. In one example, the holder is a cage, basket, net,
cartridge or case
which supports the solid controlled release composition while allowing water
to contact a
large portion of the composition. In another example, adhesive can attach the
holder to the
solid controlled release composition. In a further example, controlled release
composition
is molded around the holder. The holder can have perforations, holes or voids
to enable
water to contact a large portion of the composition and to enable the use
solution to
dispense from the holder. The holder supports the solid controlled release
composition
inside the warewashing machine. For example, adhesive may attach the holder to
the inside
of the warewashing machine. Additionally or alternatively, the holder may
attach to the
inside of the wash tub by clips, hooks, suction cups, strings, ropes or other
fastening
devices. Structures within the warewashing machine may also be used to support
the
holder. For example, the solid controlled release composition may be directly
fastened to
the machine housing or a structure within the machine design. Furthermore, the
solid
controlled release composition may be directly or indirectly held or fastened
to removable
parts associated with the warewashing or dishwashing machine, including but
not limited
to inserts, racks, baskets, dishware, plasticware, utensils and the like.
Beneficially, the solid controlled release composition does not require an
automated
= 30 dispenser or delivery device to control the dispensing of
the composition. For use, the
current solid controlled release composition can be placed in the wash tub
before the
27
CA 3060312 2019-10-29
beginning of the cycle and may be available for contact with water throughout
an entire
cycle. The solid controlled release composition may be present in the wash tub
throughout
a complete cycle, and is formulated to be present in the wash tub for more
than one cycle,
more than two cycles, and preferably for a days' worth of cycles. The current
controlled
release composition is formulated so that the active cleaning ingredients in
the solid
controlled release composition dissolve and disperse when contacted with
water, such that
the solid controlled release composition does not require an automated
dispenser or
delivery device to control the dispensing of the active ingredient(s).
When the solid controlled release composition is mixed with water the solid
controlled release composition forms an aqueous mixture of the active
ingredient(s) of the
solid controlled release composition. Beneficially, the active ingredients can
provide a two-
in-one detergent and rinse aid composition.
Methods of Use and Dispensing
The solid controlled release composition may be suitable for both industrial
and
consumer applications including, but not limited to institutional warewashing,
consumer
dishwashing, laundering, and food and beverage applications, hard surface
cleaning, clean
in place (CIP) systems, vehicle care, healthcare. Methods of using the solid
controlled
release compositions are also provided. For ease of description, the solid
controlled release
composition will be described with use in an institutional warewashing
machine. However,
one skilled in the art will recognize that the composition may also be used in
a consumer
dishwashing machine.
Beneficially, an automated dispenser or delivery system is not required to
dispense
the solid controlled release composition during a specified stage of a cycle,
such as during
the wash cycle. That is, no system or mechanism controls when the solid
controlled release
composition is added to the cycle. Instead, the solid controlled release
composition can be
placed directly inside the wash tub of a warewashing machine at the start of
the cycle (e.g.,
before the fill and/or wash cycle) and may be present throughout the cycle.
The solid
controlled release composition can be available for contact with water through
the entire
cycle. When contacted with water, the solid controlled release composition
will partially
dissolve or erode and the contents of the solid controlled release composition
will mix with
the water to form an aqueous mixture or solution. For example, the solid
control release
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composition will partially dissolve or erode when contacted with water from
the wash cycle
or rinse cycle. Water from a source other than water from the wash or rinse
cycle may also
be applied to the solid control release composition to partially dissolve or
erode the
composition or combinations of water sources may be used. The controlled
release solid
may be placed above or below the water line in the wash tub. Preferably, the
controlled
release solid composition is placed above the water line in the wash tub.
A use solution is obtained by contacting the solid composition with a water
source.
The pH of the use solution is maintained in the alkaline range through
continuous
controlled release of the solid component in order to provide sufficient
detergency
properties. In one example, the pH of the use solution is between about 7 and
about 13.
Particularly, the pH of the use solution is between about 9 and about 12. If
the pH of the
use solution is too high, for example, above 13, the use solution may be too
alkaline and
attack or damage the surface to be cleaned.
The solid controlled release composition can release the active ingredients
over
multiple wash cycles. In one example, the solid controlled release composition
is
formulated to release the active ingredient over a period of two or more wash
cycles, and
preferably over a period of at least 20 wash cycles, at least 25 wash cycles,
or greater. The
rate at which the active ingredient is dispersed can be modified by adjusting
the
composition of the solid controlled release composition, increasing or
decreasing the size
of the solid controlled release composition, changing the amount of surface
area exposed to
water, positioning the controlled solid release composition in different
spaces inside the
wash tub, or adjusting the cycle settings, such as but not limited to the
water temperature
and cycle duration. For example, increasing the weight percentage of
polysaccharide
material (or combination of polysaccharide materials) may decrease the rate at
which the
active ingredient is dispersed, increasing the number of wash cycles the solid
controlled
release composition may be used before requiring replacement.
Methods of Manufacture
In general the solid controlled release compositions can be created by
combining
the components according to various solid formation methods to provide the
homogenous
solid. In one example, each of the components are mixed and are pressed into a
solid form.
In exemplary methods, such as for small scale production, the solid controlled
release tablet
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can be pressed for 15-60 seconds at 1000 psi, or can be pressed for 1 minute
at 2000 psi.
Commercial production of the solid controlled release composition can vary by
time and
pressure, for example. In an alternative example, the components are mixed and
harden
into a solid form. The solidification process can last from a few minutes to
about six hours
depending on factors such as but not limited to: the size of the formed or
cast composition,
the ingredients of the composition, and the temperature of the composition.
The solid controlled release compositions may be formed using a batch or
continuous mixing system. In an exemplary embodiment, a single- or twin-screw
extruder
is used to combine and mix one or more ingredients at high shear to form a
homogeneous
mixture. In some embodiments, the process mixture may be dispensed from the
mixture by
forming, pressing, casting, extruding, or other suitable means, whereupon the
composition
is pressed or hardens to a solid form. The structure of the matrix may be
characterized
according to its hardness, melting point, material distribution, crystal
structure, and other
like properties according to known methods in the art. Generally, a solid
controlled release
composition processed is substantially homogeneous with regard to the
distribution of
ingredients throughout its mass and is dimensionally stable. As referred to
herein,
dimensional stability refers to a change in dimension of the solid composition
(such as
from cracking and/or swelling) greater than 3% as measured in length, height
and/or width
(depending upon the method of solidification, shape of the solid detergent
composition
and/or formulation into any type of capsule or other component for dispensing)
at the
evalulated temperature and time conditions outlined herein and at ambient
humidity of the
evaluated atmosphere. The average growth numbers in length, height and/or
width
represent the change in dimension.
By the term "solid", it is meant that the hardened solid controlled release
composition will not flow and will substantially retain its shape under
moderate stress or
pressure or mere gravity. The degree of hardness of the solid controlled
release
composition may range from that of a fused solid product which is relatively
dense and
hard, for example, like concrete, to a consistency characterized as being a
hardened paste.
In addition, the term "solid" refers to the state of the solid controlled
release composition
under the expected conditions of storage and use of the solid composition. In
general, it is
expected that the solid controlled release composition will remain in solid
form when
CA 3060312 2019-10-29 =
. .
exposed to temperatures of up to approximately 100 F and particularly up to
approximately 120 F and retains a dimensional stability.
All publications and patent applications in this specification are indicative
of the
level of ordinary skill in the art to which this invention pertains.
EXAMPLES
Embodiments of the present invention are further defined in the following non-
limiting Examples. It should be understood that these Examples, while
indicating certain
embodiments of the invention, are given by way of illustration only. From the
above
discussion and these Examples, one skilled in the art can ascertain the
essential
characteristics of this invention, and without departing fann thc spirit and
scope thereof,
can make various changes and modifications of the embodiments of the invention
to adapt
it to various usages and conditions. Thus, various modifications of the
embodiments of the
invention, in addition to those shown and described herein, will be apparent
to those skilled
in the art from the foregoing description. Such modifications are also
intended to fall
within the scope of the appended claims.
EXAMPLE 1
Various solid carbonate-based detergent compositions were evaluated for
ability of
a polysaccharide material to control release of the carbonate-based detergent.
In this
example a long chain polysaccharide, specifically sodium carboxymethyl
cellulose (CMC)
was evaluated for an ability to decrease solubility of an ash based detergent
block located
in the wash chamber of a dishmachine. Formulations in Table 2 show a combined
carbonate solid with carboxymethyl cellulose as the evaluated polysaccharide
material at
varying concentrations. The liquid premix was made as an individual unit and
added to the
solid components as a mixture.
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. .
TABLE 2
Tablet I Tablet I Tablet I Tablet I
Raw Matcrial Control
1 2 3 4
Ash 61.78 59.28 56.78
51.78 41.78
Sodium Tripolyphosphate 25 25 25 25 25
Sodium Carboxymethyl
2.5 5 10 20
Cellulose
KOH (45%) 3.59 3.59 3.59 3.59
3.59
Active Ingredients 9.63 9.63 9.63 9.63
9.63
Total 100 100 100 100 100
The formulations in Table 2 were used to make 50 gram pressed tablets. For
each
tablet, 50g of the mixture was added to a pre-fabricated mold. The powder was
compressed in the mold at 1000 PSI for 20 seconds. The tablets were removed
from the
mold and stored at room temperature until testing at least 24 hours later.
Pressed tablets of commercial ware wash detergents with portions of the dense
ash
substituted for the polysaccharide material sodium CMC at increasing
concentrations up to
20% were evaluated. The tablets were tested to see how many cycles in a
dishmachine it
took before the tablet was visibly dissolved. The tablet was held in a small
screened
enclosure above the sump on the side of the machine wash compartment, as shown
in FIG.
1. The tablets were placed in the enclosure at cycle 0 and washed
consecutively with 30
second intervals between each wash cycle. The cycle count for each tablet was
considered
the number of cycles completed prior to the tablet being visibly completely
dissolved and
no longer present in the enclosure. The testing conditions were as follows:
Machine: Hobart AM-15
Wash Temp: 155-160 F
Rinse Temp: 180-190 F
Wash Length: 45 seconds
Rinse Length: 10 seconds
As shown in FIG. 2, the inclusion of sodium CMC demonstrated a positive
correlation for the total number of cycles until the tablet was fully
dissolved. This
beneficially shows longevity of the tablet as a result of the CMC added to the
formulation.
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All formulations with CMC demonstrated an increase in total number of cycles
compared
to the control (non-CMC).
EXAMPLE 2
Additional solid carbonate-based detergent compositions were evaluated
according
to the methods and conditions of Example 1 for ability of a polysaccharide
material to
control release of the carbonate-based detergent. In this example a long chain
polysaccharide, specifically sodium carboxytnethyl cellulose (CMC) was
evaluated in an
STPP-free formulation for an ability to increase the stability and decrease
solubility of an
ash based detergent block located in the wash chamber of a dishmachine.
Formulations in
Table 3 show additional formulations combining carbonate solid with
carboxymethyl
cellulose as the evaluated polysaccharide material at varying concentrations.
TABLE 3
Tablet Tablet Tablet Tablet Tablet
Raw Material Control
1 2 3 4 5
Dense Ash 72.1 69.6 67.1 64.6 62.1 52.1
Carboxymethyl Cellulose 0 2.5 5 7.5 10 20
Active Ingredients 24.9 24.9 24.9 24.9 24.9 24.9
Water 3 3 3 3 3 3
Total 100 100 100 100 100 100
The evaluated solid compositions have a greater ash content and high liquid
content
compared to those evaluated in Example 1. Results are shown in FIG. 3 which
are
consistent with FIG. 2 showing there is an increase in cycle count, which
demonstrates
longevity of the tablet, observed while increasing CMC content compared to the
formulas
without CMC.
The solubility rate for the tablets after consecutive wash cycles was also
studied
with the addition of CMC by recording the percent weight loss after the
tablets were
completely dried. As seen in FIG. 4, the addition of CMC to the solid
formulation
contributes to a longer lifespan by significantly reducing the amount of solid
released
during each wash cycle.
33
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, =
EXAMPLE 3
Additional solid carbonate-based detergent compositions were evaluated
according
to the methods and conditions of Example 1 for ability of a polysaccharide
material to
control release of the carbonate-based detergent according to embodiments. In
this
example xanthan gum was evaluated in an STPP-free formulation for an ability
to decrease
solubility of an ash based detergent block located in the wash chamber of a
dishmachine.
Formulations in Table 4 show additional formulations combining carbonate solid
with
xanthan gum as the evaluated polysaccharide material at varying
concentrations.
ABLE 4
Raw Material Tablet 1 Tablet 2 Tablet 3
Ash 71.1 69.6 67.1
Xanthan Gum 1.0 2.5 5.0
Active Ingredients 24.9 24.9 24.9
Water 3.0 3.0 3.0
Total 100 100 100
The results of employing Xanthan Gum as the polysaccharide material for the
controlled release agent are shown in FIG. 5 and FIG. 6. A beneficial increase
to the
lifespan (also referred to as longevity) of the tablet was observed by
substituting a portion
of the builder (dense ash) with Xanthan Gum up to 10%.
EXAMPLE 4
Solid stability and swelling testing was conducted to assess the solid
controlled
release compositions. It is known that when exposed to the environment solid
composition
stability is impacted and can cause issues for both performance and
packaging/storage. In
order to assess the stability of the CMC/Xanthan Gum solid controlled release
compositions 10 formulas were stored at RT, 100 F, and 122 F for 1 week. The
formulations were sealed in a ziplock container and therefore humidity was not
directly
related. After 1 week change in dimensions (height/width) was calculated and a
change
34
CA 3060312 2019-10-29
= =
greater than 3% is considered a fail as lacking dimensional stability. As
referred to herein,
dimensional stability refers to a change in dimension of the solid composition
(such as
from cracking and/or swelling) greater than 3% as measured in length, height
and width at
the evalulated temperature and time conditions outlined herein and at ambient
humidity of
the evaluated atmosphere. The average growth numbers in length, height and
width
represent the change in dimension.
The results confirmed that as CMC concentration increased in the solid so did
the
rate of swelling and therefore a decrease in dimensional stability. Even at RT
the swelling
reached the 3% threshold beyond 15% CMC by weight. At 122T the solids were
observed
to reach the 3% threshold beyond 6% CMC by weight. No significant swelling
(>3%) was
observed when Xanthan Gum was used as the controlled release component.
Beneficially,
this indicates that Xanthan Gum is an ideal agent for controlling the release
of the solid,
however with increased Xanthan Gum the tablet becomes less and less soluble as
it is
dispensed during washing. This often results in a small (<3g) insoluble
portion remaining
in the dispense chamber. Beneficially this was not observed in CMC formulas.
CMC can
also provide boosted cleaning performance as an anti-redeposition agent,
specifically for
protein. These results also indicate the preference for combining a cellulose
polysaccharide
with the xanthan gum for the solid controlled release compositions.
EXAMPLE 5
Additional Polysaccharides and Cellulose Derivatives were evaluated, namely
branched polysaccharides. The evalulated materials included: ash control (no
polysaccharide), CMC (Sample A; Sample B), guar derivative, hydroxyethyl
cellulose
(HEC Natrosol Sample A; HEC Cellosize Sample B), and xanthan gum. The
distictions
between the evaluated CMC and HEC samples on the basis of viscosity and degree
of
substitution (DS) are shown in Table 5.
CA 3060312 2019-10-29
= .
TABLE 5
Sample Viscosity (cPs) DS
CMC A 1380 0.92
CMC B 1680 0.95
HEC A ¨2000 1.5
HEC B ¨3000 1.5
FIG. 7 shows evaluation of the polysaccharides and cellulose derivatives
evalulated
at 5% and 10% of the polysaccharide material and comparing them to the
standard ash
formula (labeled as No Polysaccharide) dispensing rate (number of cycles until
fully
dissolved). As shown, the HEC materials demonstrated greater than 150 cycles
and provide
an additional type of cellulose derivative providing improves performance of
the tablet
from a controlled release profile_ As shown, the CMC and HEC samples exhibited
a
significantly increased tablet longevity, that may be beneficial in providing
controlled
release of a solid detergent composition.
EXAMPLE 6
As set forth in the Examples 1-5 the various maximum detergent concentration
of
the homogenous controlled release tablets is limited by the detergent
dissolution rate.
Additional tablets were evaluated where the tablet consisted of two phases,
the first phase a
controlled release portion composed of the detergent composition with the
polysaccharide
material(s) (e.g. CMC and/or Xanthan) and a second phase composed of the
detergent
composition without the solw release polysaccharide material(s). These two
compositions
are mixed separately and not combined until the tablet is formed and are added
separately
in order to create 2 distinct sections. Initial trials demonstrated the basic
ash portion
dissolved within 5-7 cycles while leaving the controlled release portion to
continue
dispensing in the dishmachine for an additional 10 cycles (17 overall).
Beneficially, a two-phase controlled release composition allows the controlled
release product to be packaged in a single solid form. It is beneficial
according to the
formulations that users do not need to touch or contact the compositions from
a safety
and/or dispensing stand point, namely repeated emptying and refilling are not
necessitated
for the dishmachine during daily operation. Moreover, the 2-phase tablet gives
the
36
CA 3060312 2019-10-29
advantage of a long lasting detergent tablet with an increased amount of
detergent released
during the first few cycles due to rapid dissolution of the tablet phase not
containing
polysaccharide(s), resulting in an optimized starting detergent concentration
in the dish
machine at the start of dish washing operations. The detergent concentration
is maintained
over time by the controlled release of detergent from the controlled release
portion of the
tablet.
The evaluated formulations are shown in Table 6.
TABLE 6
Controlled
Raw Material Basic Phase Release
Phase
Ash 72.1 64.6
Sodium Carboxymethyl
Cellulose 0.0 5
Xanthan Gum 0.0 2.5
Active Ingredients 21.1 21.1
Water 6.8 6.8
Total 100 100
FIG. 8 shows the average conductivity of the use solution in a ware wash
machine
is shown as a versus the number of ware wash cycles for a single phase
controlled release
tablet and a 2-phase controlled release tablet. Since conductivity correlates
linearly with the
amount of detergent released in the use solution, the graphs demonstrate that
the
.. concentration, and thus the active detergent concentration in the use
solution, increases
more rapidly and reached a higher maximum concentration than the single phase
controlled
release tablet. FIG. 9 are images of the dissolution of a two-phase tablet
over various
cycles, with both sides of the 2-phase tablet photographed (top: controlled
release; bottom:
rapid dissolution phase). Both sides of the two-phase tablet are photographed
showing that
one side (without the polysachharide material ¨ "rapid dissolution phase") is
completely
disintegrated and the controlled release portion remains intake after 11
cycles.
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. .
EXAMPLE 7
Additional solid carbonate-based detergent compositions were evaluated
according
to the methods and conditions of Example 1 for ability of a polysaccharide
material to
control release of the carbonate-based detergent. In this example a long chain
polysaccharide, specifically sodium carboxymethyl cellulose (CMC) was
evaluated in an
STPP-containing formulation for an ability to increase the stability and
decrease solubility
of the solid carbonate-based detergent block located in the wash chamber of a
dislunachine.
Formulations of the carbonate solids with carboxymethyl cellulose (CMC) as the
evaluated
polysaccharide material at varying concentrations were compared to the xanthan
polysaccharide materials.
The evaluated solid compositions have a greater concentration of the
polysaccharide material, increasing from 0% to 20%. Results are shown in FIG.
10 which
show the CMC polysaccharide in comparison to the Xanthan data shown in FIG. 6
(discussed earlier). The figure shows the change in tablet mass (wt-%) versus
cycle for
tablets with varying amount of polysaccharides in the carbonate-based
formulations.
Beneficially, the data show that use of two distinct polysaccharide materials
are able to
provide slowed release profiles for the solid formulations.
EXAMPLE 9
Additional solid carbonate-based detergent compositions were evaluated
according
to embodiments of the compositions and dissolution rates thereof with varying
D.S. and
viscosity. The formulation in Table 7 was utilized to evaluate several CMC
polysaccharide
materials with varying DS from 0.7 to 1.3 and viscosity from about 1 cP to
about 3500 mPa
(equivalent to cP), as shown in Table 8. The additional active ingredients
include
surfactants and polymer materials (consistent in all evaluated formulations).
38
CA 3060312 2019-10-29
TABLE 7
Description Control
Ash 72.1%
Polysaccharide Material 10.0%
Additional active Ingredients 21.1%
Water 6.8%
Total 100
TABLE 8
D Viscosity Viscosity
.S
(mPa) (1%)
4 0.95 1680 1680
2 0.9 758 379
0.87 3600 3600
3 1.18 1960 980
1 1.16 300 150
5 The results are shown in FIG. 11 wherein the size and labels for each
circle correlate
to the number of cycles derived from a 50g tablet when the CMC is included at
10% of the
formula composition. The data shows the impact of both degree of substitution
and
viscosity on the tablet lifespan (or tablet longevity and ability to dose for
a number of
cycles).
The following represent non-limiting embodiments of the subject matter
disclosed
herein.
Embodiment 1. A solid controlled release composition for cleaning wares
comprising: a carbonate alkalinity source; at least one polysaccharide
material comprising
from about 0.01 wt-% to about 20 wt-% of the composition; and an active
ingredient
cleaning agent, wherein the polysaccharide material has an about 1 wt-% to
about 2 wt-%
aqueous solution viscosity (25 C) of between about 15 cps and about 5000 cps;
wherein
the solid controlled release composition is a homogenous multi-use composition
and is not
encapsulated with delayed release chemistry.
Embodiment 2. The composition of Embodiment 1, wherein the carbonate
alkalinity source is an alkali metal carbonate.
Embodiment 3. The composition of Embodiment 2, wherein the alkali metal
carbonate alkalinity source is sodium carbonate.
39
Date Recue/Date Received 2021-10-05
Embodiment 4. The composition of any one of Embodiments 1-3, wherein the
polysaccharide material(s) comprises from about 0.01 wt-% to about 15 wt-% of
the
composition.
Embodiment 5. The composition of any one of Embodiments 1-4, wherein the
polysaccharide material(s) has at least one of a degree of substitution (D.S.)
between about
zero and about 3, or a degree of polymerization between about 200 and about
15,000.
Embodiment 6. The composition of Embodiment 5, wherein the D.S. of the
polysaccharide material is measured by the number of glucose units of a
cellulose molecule
substituted with a carboxymethyl-, methyl-, ethyl-, hydroxyethyl-,
hydroxypropyl-,
hydroxypropylmethyl-, acetate, tri acetate-, acetate-propionate-, and/or
acetate-butyrate
group(s).
Embodiment 7. The composition of any one of Embodiments 1-6, wherein the
polysaccharide material is one or more of carboxymethylcellulose (CMC),
hydroxyethylcellulose (HEC), hydroxypropylcellulose (HPC), hydroxypropyl
methylcellulose (HPMC), methylcellulose (MC), cellulose acetate, cellulose
triacetate,
xanthan, and combinations thereof.
Embodiment 8. The composition of any one of Embodiments 1-7, wherein the
polysaccharide material comprises carboxymethylcellulose (CMC) and/or xanthan.
Embodiment 9. The composition of Embodiment 8, wherein the ratio of
carboxymethylcellulose (CMC) to xanthan is from about 1:110 about 30:1.
Embodiment 10. The composition according to any one of Embodiments 1-9,
wherein the active ingredient cleaning agent is a surfactant.
Embodiment 11. The composition according to Embodiment 10, wherein the
surfactant is a nonionic surfactant.
Embodiment 12. The composition of any one of Embodiments 1-11, wherein the
solid controlled release composition is a multi-use composition having a mass
of at least 25
grams.
Embodiment 13. The composition of any one of Embodiments 1-12, wherein the
solid controlled release composition is a tablet, coated tablet, puck, brick
or block, and
wherein the solid controlled release composition is a multi-use composition.
Date Recue/Date Received 2021-10-05
Embodiment 14. The composition of any one of Embodiments 1-13, wherein at
least one polysaccharide material comprises about 1 wt-% of the composition or
at least 1
wt-% of the composition.
Embodiment 15. The composition of any one of Embodiments 1-13, wherein the
carbonate alkalinity source comprises between about 40 wt-% and about 95 wt-%
of the
solid composition, the polysaccharide material comprises between about 0.01 wt-
% and
about 15 wt-% of the solid composition, and the active ingredient cleaning
agent comprises
between about 0.1 wt-% and about 40 wt-% of the solid composition.
Embodiment 16. The composition of Embodiment 15 further comprising from
about 0.1 wt-% to about 50 wt-% of an additional functional ingredient,
wherein the
additional functional ingredient is one or more of defoaming agents, anti-
redeposition
agents, anti-scale agents, bleaching agents, solubility modifiers,
dispersants, metal
protecting agents, stabilizing agents, corrosion inhibitors, additional
sequestrants and/or
chelating agents, threshold inhibitors, crystal modifiers, fragrances and/or
dyes,
hydrotropes or couplers, buffers, and solvents.
Embodiment 17. The composition of any one of Embodiments 1-16, wherein the
composition is phosphate-free.
Embodiment 18. The composition of any one of Embodiments 1-17, wherein the
solid composition is a two-phase solid, wherein a first phase is the
homogenous solid
comprising the polysaccharide materials, carbonate alkalinity source, and
active ingredient
cleaning agent, and wherein the second phase is a homogenous solid comprising
the
carbonate alkalinity source and active ingredient cleaning agent.
Embodiment 19. The composition of Embodiment 18, wherein the first phase
and/or second phase further comprise additional functional ingredients.
Embodiment 20. The composition of Embodiment 18 or 19, wherein the ratio of
the
first phase to the second phase on weight basis is from about 10:1 to about
1:10.
Embodiment 21. A method of dispensing a solid controlled release composition
according to any one of Embodiments 1-20, comprising: contacting the solid
composition
with a water source to generate a use solution of the composition; and
contacting wares
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Date Recue/Date Received 2021-10-05
with the use solution at pH from about 7 to about 13 for a sufficient amount
of time to
remove and/or solubilize soils.
Embodiment 22. A system for cleaning wares in an automatic dishwashing
environment comprising: a solid controlled release composition comprising a
carbonate
alkalinity source, at least one polysaccharide material comprising from about
0.01 wt-% to
about 20 wt-% of the composition, and a surfactant; wherein the polysaccharide
material
has an about 1 wt-% to about 2 wt-% aqueous solution viscosity (25 C) of
between about
cps and about 5000 cps; wherein the solid composition is a homogenous 2-in-1
composition providing a detergent and rinse aid in a single solid composition,
wherein the
10 solid is a multi-use composition, and wherein the solid is not
encapsulated with delayed
release chemistry; and wherein the system does not include a dispensing
system.
Embodiment 23. The system of Embodiment 22, wherein the solid controlled
release composition is a tablet, coated tablet, puck, brick or block.
Embodiment 24. The system of Embodiment 22 or 23, wherein the carbonate
15 alkalinity source is an alkali metal carbonate, wherein the
polysaccharide material
comprises one or more of carboxymethylcellulose (CMC), hydroxyethylcellulose
(HEC),
hydroxypropylcellulose (HPC), hydroxypropyl methylcellulose (HPMC),
methylcellulose
(MC), cellulose acetate, cellulose triacetate, and xanthan, and wherein the
active ingredient
is a nonionic surfactant, chelants and/or enzyme.
Embodiment 25. The system of Embodiment 24, wherein the polysaccharide
material comprises carboxymethylcellulose (CMC) and xanthan, and wherein the
ratio of
carboxymethylcellulose (CMC) to xanthan is from about 1:1 to about 30:1.
Embodiment 26. The system of any one of Embodiments 22-25, wherein the
polysaccharide material(s) comprises from about 0.01 wt-% to about 15 wt-% of
the
composition.
Embodiment 27. The system of any one of Embodiments 22-26, wherein the solid
composition is a pressed solid and wherein the automatic dishwashing
environment is a
consumer or commercial dish washing machine.
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Date Recue/Date Received 2021-10-05
Embodiment 28. The system of any one of Embodiments 22-27, wherein the at
least one polysaccharide material comprises about 1 wt-% of the composition or
at least 1
wt-% of the composition.
The inventions being thus described, it will be obvious that the same may be
varied
in many ways. Such variations are not to be regarded as a departure from the
spirit and
scope of the inventions and all such modifications are intended to be included
within the
scope of the following claims. The above specification provides a description
of the
manufacture and use of the disclosed compositions and methods. Since many
embodiments can be made without departing from the spirit and scope of the
invention, the
invention resides in the claims.
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Date Recue/Date Received 2021-10-05
